Method for manufacturing of specification paving and industrial asphalts



April 30, 1963 L W. CORBETT ETAL PAVING AND INDUSTRIAL ASPHALTS Filed Dec. 21, 1959 FlGURE- METHOD FOR RECONSTITUTING S SheetsSheet 1 ASPHALTS BY REFLUXING ASPHALTENES f 1 (i l -P/S RESID. 5 8 2 4 v 6 PRIM'ARY WA'SH MIXING HEAD CENTRIFUGE CENTRIFUGE n-HEXANE L7 STORAGE} BENZENE n- HEXANE STORAGE) TO STORAGE] FLASH\ TOWER I3 I ll |0 HEAT TO STORAGE l5 MXING SOLVENT T0 HEAD REFRACTIONATER l7 {FLASH I6\ T TOWER HEA RECONSTITUTED w ASPHALT Luke W. Corbeh Clark E. Adams lnvenTOfS Glen P. Humner By WW 27% Patent Attorney,

April 30, 1963 Filed Dec. 21, 195%:-

SOFTENING POINT F.

- L. W. CORBETT ETAL METHOD FOR MANUFACTURING OF SPECIFICATION PAVING AND INDUSTRIAL ASPHALTS 3 Sheets-Sheet 2 FIGURE'Z ASPHALTENE RECONSTITUTED ASPHALTS ARE INTERMEDIATE TO THOSE PREPARED BY AIR BLOWING AND STRAIGHT REDUCTION I I I I I I I I I AIR BLOWN RECONSTITIJTED x STRAIG2T\\ H REDUCED x\ I l I M8) Luke W. Corbefl Clark E. Adams Glen P. Humner By WW. ZZ J Inventors Porenf Arrorney PENETRATION (IOO g., 5 sec.)

April 30, 1963 Filed Dec. 21, 1959 METHOD FOR MANUFACTURING OF SPECIFICATION L w. CORBETT EI'AI. 3,087,887

PAVING AND INDUSTRIAL ASPHALTS 5 Sheets-Sheet 3 FIGURE-3 RECONSTITUTED ASPHALT DISPLAYS BETTER PENETRATION TEMPERATURE SUSCEPTIBILITY THAN ASPHALT FLUXED FROM THE SAME BASE I I I I I x RECONSTITUTED III FLUXED I I l I I Glen P. Hamner Patent Attorney United States Patent Filed Dec. 21, 1959, Ser. No. 860,857 8 Claims. (Cl. 208-45) This invention relates to a new and improved method of making asphaltic compositions. More specifically, the invention teaches the adding of extraneous asphaltenes into asphalt to improve its properties.

In the past and presently, two methods are employed to produce high quality asphalts which are needed for road paving and other applications where high constancy is of the essence. One method involves a two-stage distillation operation. Ordinarily, the first stage is a conventional steam distillation performed in an atmospheric pipe still to remove the bulk of the light fractions from the crude. The second stage, needed to further concentrate the heavy constituents, is a vacuum distillation, with or without the presence of steam. Air blowing of pipe still residuum is the second method used currently. In the latter process the aromatic oils are chemically converted to asphaltenes by oxidation. Both of the above methods have significant drawbacks. The first requires the costly second stage vacuum distillation. This operation requires the expenditure, conservatively estimated, of from 15 to 20 per barrel in addition to equipment costs.

In the vacuum process, the percent of asphaltenes is increased by concentration, whereas in the air blowing process, the percent of asphaltenes is increased by conversion from aromatic oils. This increase in percent asphaltenes is largely responsible for the increase in consistency of the resulting asphalt product.

In the manufacture of heavy fuel oils, it is common practice to visbreak a residual stock in order to meet lower viscosity requirements. This in essence is a mild form of cracking or heat soaking which has a tendency to thermally crack both asphaltenes and oils to make the less viscous product desired to meet fuel specifications. Since asphaltenes are largely responsible for high consistency or viscosity, it is working at cross purposes to make asphaltenes in one process to increase consistency while visbreaking in another to reduce this.

Asphalt-bearing crudes normally contain from 4 to 12% by weight of asphaltenes. Since there is a greater excess of asphalt crudes than of non-asphaltic crudes, there exists an ever abundant source of asphaltenes.

There is also a demand for large volumes of heavy fuel oils which must be made by visbreaking or by dilution with more valuable lighter petroleum oils. This offers the opportunity to divert asphaltenes to asphalt applications where consistency is desired and to free deasphaltened oil (petrolenes) for other uses such as in heavy fuels.

In the case of specialized industrial asphalts, specific advantages may be obtained over the conventional air blown asphalts. For example, the blended asphalts have improved ductility and staining properties. In paper laminating asphalts stain is of utmost significance.

In accordance with this invention, it has been found that an asphalt having properties comparable to those produced by conventional process and, in some respects even better, is obtained by adding or blending an extraneous asphaltene fraction into a residuum. Briefly, this process consists of deasph-altening a particular residuum, i.e. removing the asphaltenes, and subsequently refluxing the asphaltenes into the same or different residuum.

The percentage of asphaltenes added varies from 2 to 50% by weight. With an average residuum, it takes 3,087,887 Patented Apr. 30, 1963 at least 2% to accomplish any effective increase in consistency. For paving, the addition is normally on the order of from 5 to 15% to obtain an asphalt of the proper consistency. For certain industrial asphalts, the addition is of the order of 10 to 50% depending upon the product desired. The products to which over 50% have been added are normally of such a high softening point that they are unsuitable for most applications.

FIGURE 1 illustrates a preferred process of obtaining asphaltenes and their subsequent blending with residuum.

FIGURE 2 graphically compares the penetrationsoftening point relation between the asphalt blend of the invention with both air blown and straight reduced asphalt.

FIGURE 3 shows the temperature susceptibility of the asphalt blend and asphalt fluxed with the same base.

Turning now to FIGURE 1, pipe still residuum from Tia Juana medium crude (35% by volume on crude) kept in storage 1 is pumped through line 2 while normal hexane from storage 3 is pumped into the same line. The mixing ratio is preferably 5.0 solvent to oil by volume, although this may vary from 3.0 to 25.0. The lower ratios are preferred from the practical volume handling standpoint although higher ratios permit greater selectivity. Other solvents such as pentane, isopentane, normal heptane, isooctane, or other paraflin type pure or mixed solvents may also be used. As soon as the residual stock is contacted with the solvent in this ratio, the asphaltenes are deflocculated, that is, the asphaltene-oil phase colloid is broken up by virtue of dilution. The mixture then passes through a mixing head 4 or some other suitable continuous mixing device and thence into a continuous type high speed centrifuge 5. A centrifuge suitable for this purpose is a Sharples Nozzlejector type DH-2 which is capable of handling up to 3000 gallons per hour of charge. For greater capacities a battery of centrifuges may be used. The asphaltene-hexane slurry is rejected from the centrifuge and consists of approximately equal volumes of asphaltenes and hexane-oil. The slurry is then further diluted with additional hexane through line 7 to a solvent to asphaltene ratio of about 4.0. This mixture is then passed into the Wash centrifuge where a second separation is made. The asphaltenes are are again rejected in about a 1.0 ratio and moved into line 12 for further processing. The combined solvent-petrolene oil mixtures are continuously passed through a heat exchanger 10 and to a flash tower 11 for stripping. The petrolenes are thus recovered as a residual product, and the solvent is returned to storage for reuse.

The asphaltene slurry passing through line 12 is then mixed with benzene from storage 13 and into a mixing head 14 in a volume ratio of about 3 :1, slurry to benzene. this causes solution of the asphaltenes in the solvent mixture. After a small amount of mixing, a fresh charge of residuum is mixed continuously with the asphaltenebenzene-hexane mixture through line 15. The higher temperature of the residuum from storage imparts a higher temperature to the above mixture to F.) thus affecting better solution and mixing. In this example the same Tia Juana residuum was used, however, as previously stated, this residuum may be another stock de pending upon the end product desired. The proportion of the residual stock to the slurry also depends upon the end product desired as will be brought out in blending data to follow. Solution is effected during mixing after which the mixture is passed into a heat exchanger 16 and then to a flash tower 17. The solvent is thus refractionated and the blended asphalt recovered through line T8 as the flash tower residuum. It has also been demonstrated by laboratory blending and stripping that other solvents can be used in place of benzene to facilitate the mixing of asphaltenes. For example, the same net result can be obtained by using straight run petroleum naphtha boiling between 300 and 400 F., other paraifinic distillates, and other aromatic solvents such as xylene, tolu- 4 duced in the same figure. By taking the same original residuum or flux and blending it to contain increasing amounts of extraneous asphaltenes, a third relationship was obtained as shown by the curve marked reconstimixtures Themof- Solvents y 3150.136 of an 5 tuted. The technique used for manufacturing this asphalt Orlgln outsiqe Petroleum, those obtfllfled cm was the same as that previously described. Table I shows coal carbonlzatlon pf The y reqmrements of properties of the asphalts produced by the three methods. the solvent are that It must have Fufiielent solvent Power The properties of the asphalts produced are illustrated for asphaltenes, and have a sufiiciently low bo1l1ng point Clearly in FIGURE 2 and the data below. to permit fractionation from the reconstituted asphalt The data illustrate how the blended asphalts are inter- It Is also 199 9 to Incorporate the esphaltenes mediate in such properties as low temperature penetration asphalt byfmxmg wlthoPt a Solvent Thls method avolds susceptibility, penetration index, ductility and stain. It the neeessltY of removing e solvent from the blendwill be noted that the blended asphalts are less susceptible Howeveflthls Procedure f e very hlgh temperatures to temperature than straight reduced while having satisand addmonal Power f factory ductility for paving. All the reconstituted asphalts A 1PhalteneS3 a mfusable, brown'blaek matenal were negative to the Oliensis spot test (Standard Test havmg Speelfie grevlty of q' 9 2 g may be Method Tl02-42, American Association of State Highfiefined as that Porno of a reslduum Whlee 1s Insoluble way Ofiicials), which indicates satisfactory homogeneity. in petroleum solvents that are composed entirely of open- The column showing percent asphaltenes over flux in cham hydrocarbons Wlth a gravlty of 36 Ballme, Table I represents the difference in asphaltene percentage and at least of whose constituents boil between f h product cempared with h base flux or Original and 150 F. Pure Solvents u h as n-pe n n-heXane, residual stock. The air blown asphalts contain more n-heptane and isooctane accomplish essentially the same asphaltenes at a given penetration level compared with separation and have the advantage of uniformity of sol- 2r reconstituted and straight reduced. It will also be noted vent composition. See also Abraham, Asphalt and Allied that the asphaltene content of the reconstituted asphalts Table I Percent Pene- Pene- Pene- Soften- Pene- Duc- Barber Asphaltration Process tration tratlon ing tration tility stains tenes 77 32 392 point index 77 over flux Air Blown 32 42 0. 2 100+ 2% 8.5 Blended 28 41 118 0. 2 100+ 2 7. 0 Straight reduced 26 39 118 0. 2 100+ 2 2.6 Air Blown 28 40 1. 2 1s 3 10. 5 23 31 127 0.2 83 2 9.0 21 30 125 -0. 1 100+ 2 4. 0 1a 17 190 3.7 3.5 3% 18.5 10 13 150 1. 1 0. 0 2 16.3 10 13 147 0.2 50 2 5.0

Substances, D. Van Nostrand Co., New York (1945), pp. 71 and 1165.

The following examples further show the advantages of the instant invention.

EXAMPLE 1 A Tia Juana crude flux residuum was air blown at 450 to 500 F. by conventional techniques; a series of products were obtained at different times of blowing. The tested softening points were plotted against the penetration of the successive products yielding the curvilinear relationship shown in FIGURE 2. The same flux or residuum was reduced by vacuum distillation to various levels of hardness (which varies with the temperature and processing rate), obtaining products of varying softening point EXAMPLE 2 As to industrial asphalts such as under Federal Specification SSA666 which covers purchases made through the Federal Standard Stock Catalog, the blended asphalts pass those specifications normally made by air blown asphalts.

7 Type I asphalt as shown below may be prepared by blending a Tia Juana flux (containing 13% by weight of asphaltenes) with asphaltenes to bring its content up to 25%. Type II can be prepared by the same process to and penetration. The curve from this relationship was obtain a product of 28% asphaltenes. Type III is a then plotted as shown by the line marked straight reproduct of 27% asphaltenes.

Table II Type I Type II Type III Speeifi- Blended Speeifi- Blended Speeifi- Blended cation cation cation Softening Pt.,F.. -165 -165 153 140-171 151 Penegr tlt tign:

25-50 40 20-50 30 25-50 31 ifi5 Ff 10+ 13 158+ 11 10+ 12 Duetility k 90 100 95 77 F. 6+ 50 4+ 15 15+ 20 Usage surfaced Flat; Unsurtaeed Vlaterproofing,

Built-up Roof Built-up R001 Dampproofing EXAMPLE 3 To prove the adaptability of the invention to another crude and to interchange the asphaltenes between base stocks, additional blends were made. Here it will be stage reduction methods or by semi-blowing, may be replaced. In essence, the desired increase in consistency can be obtained by adding asphaltenes rather than distilling off volatile oils or converting heavy aromatic fractions b air blowin noted that negative spot asphalts can be blended by use 5 Thegbove examiles are only illustrative of the instant of asphaltenes from &11 blown asphalt as well as trom invention and should not be construed as ,dgfinitive. ditterent crude sources. The asphalts in these examples What i claimed fall within paving grades specification in some cases and 1. A process for preparing an improved asphalt which in the lighter industrial grades in others. process comprises contacting a petroleum fraction con- Table III Soften- Penetration Ducpercent; Flux from Asphaltenes ing tility Oliensis Asphalcrude from point, 77 spot tenes over F. @77 @32 flux Lagunillas- Lagunillas. 134 47 18 100+ Neg..-" 12.3 Do TiaJuana 116 95 31 100+ Neg.. 6.0 Do do 137 43 15 92 Ncg.. 13.0 Tia Juana -do 129 57 18 100+ Neg.. 10.5

1 From 220 F. blown coating asphalt.

EXAMPLE 4 taining asphaltenes with a liquid parafiin into which said This example clearly shows how temperature suscep- :Isphaltenes pllecipitats as f i l a asphal' enes from sa1d fraction slurried in sa1d l1qu1d paraflin, tiblhty may be Improvad. by blending Wlth asphaltenes separating said asphaltenes from said parafiin, admixing 1he fluxefi.asphalt contams 85% of pqnetmtlon said asphaltenes with a hydrocarbon solvent, blending l preclpltaited base zlsPhalt'sand Mldifle East lube the resulting solution of asphaltenes with an asphalt distillate i gg T 2? g g s residuum containing both asphaltenes and petrolenes and z gg i g gl g t i g separating said hydrocarbon solvent from the resulting a; gpg fi s iy i was ma 6 o appro m y improved asphalt, said solution of asphaltenes being Of the two asphalts, the blended one contains a slightly $2 ,213: g g ig igg g {3 22 2 i; lg csuch higher percentage of asphaltenes. Quite noticeable, howprises i 2 to 50 Wt ercentp s :3 g ever, is the better penetration temperature susceptibility asphalt P p as slmwn m E; shows g 'bleldmg 2. A process in accordance with claim 1 wherein said possltfle by use of er 2 8 mm 9 er cm es 40 hydrocarbon solvent boils at a temperature below about that nnprovement in physical properties may also be 0 R o taln EXA PLE 5 3. A process for preparing an improved asphalt which M process comprises contacting an asphalt residuum con- That blending of asphaltenes yields a product superior ta ning both petrolenes and asphaltenes with a liquid parafto h b i d b bl di other i il t i l i fin into which said asphaltenes precipitate as solids, sepashown by the following data. Propane precipitated rating said asphaltenes from said petrolenes slurried in h lt was bl d d ith Ti J n di flux t bt in said liquid parafiin, separating said asphaltenes from said a product having penetrations at 77 F. of 92, 65 and 25. liquid paraffin, dissolving said asphaltenes in a single ring Th bl d were h t t d f penetration at 32, aromatic solvent, blending the resulting solution of aspenetra-tion at 39.2, softening point and penetration Phaltelles With an asphalt residuum Containing both index. The following table show-s the data obtained. Petrolefles and asphaltenes and separating Said aromatic Table IV solvent from the resulting improved asphalt, said dissolved asphaltenes being blended with said asphalt residuum in an amount such that the resulting added asggg Process Penetratmn ggg 5 33 phaltenes comprise about 2 to 50 wt. percent of said @77 F. F index improve-d asphalt.

@320 @392 4. A process in accordance with claim 3 wherein said solvent is benzene. 2:11:11: l r tiii ri ei i- 2% 25 5. A rocess in accordance with claim 3 wherein said 25 tated Asphalt. 7 11 143 -0.2 added asphaltenes comprise 5 to 15 wt. percent of said improved asphalt. By comparing the results in this table those shown 6. A PI'OCCSS in accordance claim 3 wherein said in Table I it is apparent that an inferior product is obliquid paraficln is hexanetained. In all cases both the penetration at 32 and that A Process in accordance with claim 3 wherein said at 392 t considerably less than that obtained with solidasphaltenes are separated from said petrolenes by the blended asphalt or for that made with the asphalt centnfugmgobtained by the conventional processes. Likewise the A Process, for P P an'lmproved asphalt which softening point for each of the penetrations is inferior Process compnses admlxmg hquld Raraffin wmaining to that obtained with the other asphalts shown in Table I. 5 8 carbon P molecule Wlth a fil'st ph l On all counts the susceptibility of the propane-deasphalted reslduum contalnmg asphaltelies t P 0161165, P 1 blend is Poorer than .that f tha straight reduced, h tating solid asphaltenes m-to sa1dliqu1dparaffin, separating most ati fa t f h h a slurry of said asphaltenes in said liquid parafiin from By following the teaching of the instant invention, said first asphalt residuum, separating said asphaltenes certain industrial asphalts now made by air blowing, from said liquid parafiin, admixing said asphaltenes with along with certain paving asphalt-s now made with two a single ring aromatic solvent, blending said asphaltenes 7 8 and said aromatic solvent with a second asphalt residuum 2,862,869 Ilhnan Dec, 2, 1958 containing both asphaltenes and petrolenes and separating 2,940,920 Garwin et a1. June 14, 1960 said aromatic solvent from the resulting blend, the asphaltenes added to said second asphalt residuum by said FOREIGN PATENTS blending being of an amount such that they comprise 2 5 800,144 France Apr. 20, 1936 to 50 wt. percent of said resulting blend. 766,452 Great Britain Jan. 23, 1957 References Cited in the file of this patent OTHER REFERENCES UNITED STATES PATENTS Ellis: Chemistry of Petroleum Derivatives, vol. II,

2 131 5 Wells et 1 Sept 7 1933 10 P 1201, Reinhold 1937- 

1. A PROCESS FOR PREPARING AN IMPROVED ASPHALT WHICH PROCESS COMPRISES CONTACTING A PETROLEUM FRACTION CONTAINING ASPHALTNESS WITH A LIQUID PARAFFIN INTO WHICH SAID ASPHALTNESS PRECIPITATE AS SOLIDS, SEPARATING SAID ASPHALTENES FROM SAID FRACTION SLURRIED IN SAID LIQUID PARAFFIN, SEPARATING SAID ASPHALTNESS FROM SAID PARAFFIN, ADMIXING SAID ASPHALTENES WITH A HYDROCARBON SOLVENT, BLENDING THE RESULTING SOLUTION OF ASPHALTENES WITH AN ASPHALT RESIUUM CONTAINING BOTH ASPHALTENES AND PETROLENES AND SEPARTING AND HYDROCARBON SOLVENT FROM THE RESULTING IMPROVED ASPHALT, SAID SOLUTION OF ASPHALTENES BEING BLENDED WITH SAID ASPHALT RESIDUUM IN AN AMOUNT SUCH THAT THE ASPHALTENES ADDED TO SAID ASPHALT RESIDUUM COMPRISES ABOUT 2 TO 50 WT. PERCENT OF SAID IMPROVED ASPHALT. 